CN102286293B - Method for processing shale oil - Google Patents
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Abstract
The invention relates to a method for processing shale oil, which comprises the following steps of: ensuring refined shale heavy oil to be contacted with a first strand of catalytic cracking catalyst in a catalytic cracking reactor to perform a catalytic cracking reaction, introducing a reaction product into a fractionation system to carry out separation, and introducing the catalyst obtained after the reaction into a catalytic cracking catalyst regenerator to regenerate after carrying out stripping on the catalyst; and ensuring gasoline fraction obtained by separation of the fractionation system to be contacted with an adsorbent under the conditions of a temperature of 200 to 400 DEG C, a pressure of 0.1 to 1.0MPa, a weight ratio of the catalyst to the gasoline fraction of 0.5 to 50 and a weight hourly space velocity of the gasoline fraction of 0.1 to 10h-1, separating the contacted adsorbent and gasoline, and introducing the separated adsorbent into the catalytic cracking catalyst regenerator, wherein the adsorbent is the catalytic cracking catalyst. Due to the adoption of the method for processing the shale oil, which is provided by the invention, the nitrogen content in a gasoline product can be reduced and olefin and light arenes can be produced by the shale oil.
Description
Technical field
The present invention relates to a kind of method for processing shale oil, relate to furtherly the method for utilizing shale oil recovery propylene and light aromatic hydrocarbons.
Background technology
Shale oil be resinous shale after hot-work, the product that its organic decomposes generates, similar natural oil, but contain more unsaturated hydrocarbons than natural oil, and the non-hydrocarbons organic compound such as nitrogenous, sulphur, oxygen.Whole world oil shale reserves is approximately equivalent to 4 000 hundred million tons of shale oil, and considerably beyond natural oil total reserves, China's oil shale resources are very abundant, and its reserves occupy the 4th, the world, are equivalent to 16,000,000,000 tons of shale oil.Shale oil industry is an important component part of energy industry, also be a kind of supplementary energy of natural oil, yet at present shale oil is except on a small quantity for the production of pharmaceutical chemicals, major part is directly sold as oil fuel without secondary processing, is therefore necessary that exploitation efficiently utilizes the technology of shale oil.
US4342641 discloses a kind of method for processing shale oil, first full cut shale oil is carried out to hydrotreatment, hydrotreatment generates the cut of 249 ℃ of being less than obtaining after oil content heats up in a steamer can be directly as rocket engine fuel, and the cut of 249 ℃ of being greater than obtaining carries out hydrocracking again, to produce rocket engine fuel.Wherein hydrotreatment is carried out in two steps, first with the low catalyzer of Ni-Mo content, carries out pre-refining, more further refines with the high catalyzer of Ni-Mo content.The method hydrogenation process is many, and hydrogen consumption is high, and process cost is high, and construction investment is high.
CN1011067089A discloses a kind of working method of shale oil, shale oil first obtains hydrogenated oil through hydrotreatment, hydrogenated oil is separated into hydrogenation heavy oil and light-end products, hydrogenation heavy oil obtains dry gas, liquefied gas, gasoline, diesel oil and catalytic heavy after catalyzed conversion, and diesel oil can return to hydrotreating step.The method mainly proposes shale oil to carry out hydrofining, and the refining heavy oil obtaining, as the raw material of existing catalytic cracking technology, changes into light-end products.The gasoline nitrogen content that the method obtains is higher.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of novel method of shale oil processing.
The invention provides a kind of working method of shale oil, comprise: make refining shale heavy oil contact and carry out catalytic cracking reaction with first strand of catalytic cracking catalyst (being called for short first strand of catalyzer) in catalytic cracking reaction device, it is separated that reaction product is introduced fractionating system, introduces the regeneration of catalytic cracking catalyst revivifier after reacted catalyst stripping; The gasoline fraction that fractionating system separation is obtained and sorbent material are that 200～400 ℃, pressure are that the weight ratio of 0.1～1.0MPa, catalyzer and gasoline fraction is 0.5～50, the weight hourly space velocity of gasoline fraction is 0.1～10h in temperature
-1lower contact, the sorbent material after contact is separated with gasoline, and the sorbent material after separation is introduced described catalytic pyrolysis revivifier regeneration, and described sorbent material is catalytic cracking catalyst.
The present invention also provides a kind of process for purification of nitrogenous pyrolysis gasoline, comprises by gasoline fraction and sorbent material being that 200～400 ℃, pressure are that the weight ratio of 0.1～1.0MPa, catalyzer and gasoline fraction is 0.5～50, the weight hourly space velocity of gasoline fraction is 0.1～10h in temperature
-1lower contact, the sorbent material after contact is separated with gasoline, and the sorbent material after separation is introduced revivifier regeneration; Described sorbent material is catalytic cracking catalyst.
Method for processing shale oil provided by the invention, the refining heavy oil catalytic pyrolysis obtaining after hydrogenation of shale oil is refining, pyrolysis gasoline is carried out to refining with adsorbents with catalyst for cracking, greatly reduce nitrogen content and sulphur content in pyrolysis gasoline, thereby can reduce for example load of hydrofining or adsorption desulfurize of subsequent disposal; Catalyst for cracking after absorption returns to cat-cracker regeneration, does not need to build separately the regenerating unit of sorbent material, greatly simple flow.In addition, adopt shale oil catalytic cracking combination technique of the present invention by shale oil recovery low-carbon alkene and light aromatic hydrocarbons, can be by shale oil highly selective be converted into low-carbon alkene and light aromatic hydrocarbons.
Nitrogenous pyrolysis gasoline process for purification provided by the invention, employing cracking catalyst is sorbent material, can greatly reduce the nitrogen content of the rear gasoline of absorption, has beyond thought denitrification effect, is the sulphur content that can also significantly reduce gasoline unexpectedly; In addition, described nitrogenous pyrolysis gasoline process for purification, can be combined with cracking technique, utilizes the regenerating unit regeneration of catalytic cracking, and flexible operation, can according to circumstances regulate the consumption of sorbent material, improves denitrogenation and sweetening effectiveness.
Accompanying drawing explanation
Fig. 1 is a kind of embodiment schematic flow sheet of the present invention, wherein:
1-hydrogenation of shale oil refining plant;
2-hydrofining shale oil tripping device;
3-refines shale heavy oil catalytic pyrolysis device;
4-catalytic pyrolysis product separation device;
5-catalytic cracking gasoline refining with adsorbents device;
6-catalytic pyrolysis adsorption gasoline hydro-refining unit;
7-catalytic pyrolysis hydrofined gasoline extraction plant.
Fig. 2 is the schematic flow sheet of a kind of catalytic cracking reaction device of the present invention, wherein:
1-heavy oit pyrolysis riser reaction zone,
The transfer lime of 11-1 conveying regenerated catalyst (first strand of catalytic cracking catalyst) to riser reaction zone,
Regenerated catalyst flowrate control valve on 12-transfer lime 11,
The stock oil feed nozzle of 13-riser reaction zone 1,
The sparger of the outlet of 14-riser reaction zone 1;
The catalyst transport of 2-3 conveying regenerated catalysts (second strand of catalytic cracking catalyst) to fluidized bed reaction zone,
The transfer lime of 21-3 conveying regenerated catalysts to fluidized bed reaction zone,
Catalyst stream control valve on 22-transfer lime 2,
23-transfer lime 2 outlet spargers (can adopt existing sparger, for example inverted L shape);
3-fluidized bed reaction zone,
31-fluidized bed reaction zone bottom feed pipeline;
4-settling vessel,
41-primary cyclone,
42-secondary cyclone;
5-stripper,
Baffle plate in 51-stripper 5,
The reclaimable catalyst transfer lime of 52-stripper 5,
Reclaimable catalyst flowrate control valve on 53-transfer lime 52;
6-revivifier;
In figure, catalytic cracking reaction device (compound reactor) comprises riser reaction zone 1 and fluidized bed reaction zone 3, and transfer lime 2 is for inputting second strand of catalyzer to reactor.This schematic diagram is simple flow, but this does not affect those of ordinary skills' the understanding of the present invention.
Embodiment
Of the present invention make refining shale heavy oil and catalytic cracking catalyst under catalytic pyrolysis condition in catalytic cracking reaction device contact reacts, can carry out according to existing method, conventionally, to refine after shale heavy oil is preheated to 150～400 ℃ and introduce riser reactor, 480～630 ℃ preferably 500～600 ℃ of temperature, pressure 0.15～0.3MPa is 0.18～0.28MPa (absolute pressure) preferably, the weight ratio of catalyzer and refining shale heavy oil feedstock is 4～30, reaction times is 0.5～6s, preferably under the condition of 1～4s, contacts, reacts with hot regeneration catalyzing catalyst for cracking.
In order to utilize shale oil recovery propylene and light aromatic hydrocarbons, catalytic cracking reaction device of the present invention at least comprises a riser reaction zone and a fluidized bed reaction zone of connecting with described riser reaction zone, refining shale heavy oil is introduced fluidized bed reaction zone (also can be described as fluidized-bed reactor) after introducing riser reaction zone (also can be described as riser reactor) and introducing first burst of catalytic cracking catalyst contact reacts of riser reaction zone and is reacted, to improve propylene and light aromatics yield.Wherein, first strand of described catalytic cracking catalyst is preferably containing modified beta zeolite; The temperature of reaction of riser reaction zone is 480～620 ℃ preferably 500～600 ℃, pressure 0.15～0.3MPa is 0.18～0.28MPa (absolute pressure) preferably, the weight ratio of catalyst for cracking and refining shale heavy oil feedstock is 4～30, and the reaction times is 0.5～6s, preferably 1～4s; The reaction conditions of fluidized bed reaction zone comprises: temperature of reaction is 480～630 ℃ preferably 500～610 ℃, weight hourly space velocity 0.2～30h
-1preferred 0.5～20h
-1.Preferably, after being contacted in riser reaction zone with catalyst for cracking, introduces by refining shale heavy oil the bottom of fluidized bed reaction zone, the reacted oil gas in fluidized bed reaction zone is from the Base top contact of fluidized bed reaction zone, stripper stripping is drawn and introduced to reacted catalyzer from the bottom of fluidized bed reaction zone, then introduces revivifier regeneration.In order further to improve the productive rate of catalytic pyrolysis propylene and light aromatic hydrocarbons, from the preferred top in middle part or top of fluidized bed reaction zone, introduce second strand of catalytic cracking catalyst (being called for short second strand of catalyzer), more preferably from the top of fluidized bed reaction zone, introduce second strand of catalytic cracking catalyst, second strand of catalytic cracking catalyst is 2～10: 1 with the weight ratio of introducing the refining shale heavy oil of the first reaction zone.From the top of fluidized bed reaction zone, introduce second strand of catalytic cracking catalyst, catalyzer can be caused to top, fluidized bed reaction zone (fluidized-bed bed top charge level) locates, or described catalyzer is caused to the top at top, fluidized bed reaction zone, make catalyzer by the effect of gravity, be settled down to the top of fluidized bed reaction zone, then enter in fluidized bed reaction zone.
In method for processing shale oil provided by the invention, first strand of described catalytic cracking catalyst, second strand of catalytic cracking catalyst and sorbent material are identical catalytic cracking catalyst.Described catalytic cracking catalyst preferably contains the β zeolite of modification, and the β zeolite of described modification contains phosphorus and transition metal M, and described transition metal M is selected from one or more in Fe, Co, Ni and Cu, more preferably Fe and/or Cu.The β zeolite of described modification can be purchased or adopt various existing method preparations, such as introducing phosphorus and described transition metal M in the process at synthetic β zeolite, or after synthetic β zeolite, adopt the steps such as ammonium exchange, phosphorus modification, described transition metal M modification and calcination process to introduce phosphorus and described transition metal M.
Preferably, the gross weight of catalyzer of take is benchmark, and the described catalytic cracking catalyst containing modified beta zeolite contains the preferably preferred preferred clay of 0～60 % by weight of the heat-resistant inorganic oxide of 10～70 % by weight and 0～70 % by weight of zeolite mixture, 5～99 % by weight of 10～50 % by weight of 1～60 % by weight.The gross weight of described zeolite mixture of take is benchmark, in described zeolite mixture, contain 1～75 % by weight by the β zeolite of phosphorus and transition metal M modification and the zeolite with MFI structure of 25～99 % by weight.The zeolite of the described MFI of having structure is the supersiliceous zeolite with pentasil structure, be selected from one or more in ZSM-5 and ZRP series zeolite, be particularly selected from the ZRP zeolite (CN1147420A) of ZRP zeolite (CN1052290A, CN1058382A, US5232675) containing rare earth, phosphorous ZRP zeolite (CN1194181A, US5951963), phosphorous and rare earth, one or more in phosphorous and the ZRP zeolite (CN1211469A, CN1211470A, US6080698) of alkaline-earth metal and the ZRP zeolite (CN1465527A, CN1611299A) of phosphorous and transition metal.The zeolite of the described MFI of having structure can adopt commercially available product, also can adopt the whole bag of tricks well known in the art to be prepared, and is not repeated herein.Described heat-resistant inorganic oxide is selected from SiO
2and/or Al
2o
3; Clay is selected from kaolin and/or halloysite.Described catalyst for cracking can be according to existing method preparation.
First strand of described catalytic cracking catalyst, second strand of catalytic cracking catalyst and sorbent material, can be that this catalytic cracking catalyst participates in the regenerator obtaining through regeneration after scission reaction, also can be the mixture of regenerator and fresh dose, first strand of catalytic cracking catalyst is the mixture of regenerator or regenerator and fresh dose, and second strand of catalytic cracking catalyst is the mixture of regenerator or regenerator and fresh dose; Sorbent material is the mixture of regenerator or regenerator and fresh dose.
In order to improve low-carbon alkene particularly productive rate and the light aromatics yield of propylene, by C4～C8 hydrocarbon, (C4 hydrocarbon refers to the hydrocarbon that in molecule, carbonatoms is 4, the like) introduce in riser reaction zone or fluidized bed reaction zone and further transform, or by C4～C8 hydrocarbon in second strand of catalyst transport with the mixture contact reacts of regenerator or regenerator and fresh dose (second strand of catalyst transport in this case, be called again transfer lime reactor) after, catalyzer is introduced to fluidized bed reaction zone.In transfer lime, C4～C8 hydrocarbon and hot regeneration catalyzing catalyst for cracking are 520～680 ℃ preferably 540～650 ℃ of temperature, pressure 0.15～0.3MPa is 0.18～0.28MPa (absolute pressure) preferably, second strand of catalyzer and C4～C8 hydrocarbon weight ratio (agent-oil ratio) are 10～50, reaction times 0.05～4s is contact under the condition of 0.1～3s, reaction preferably, and reacted catalyzer (as second strand of catalyzer) is introduced fluidized bed reaction zone.Described C4～C8 hydrocarbon is preferably C 4 fraction and the light gasoline fraction that refining shale heavy oit pyrolysis product of the present invention obtains through fractionation, also can be C4～C8 hydrocarbon that is rich in alkene that other device produces, described in be rich in olefin(e) centent in C4～C8 hydrocarbon of alkene and be not less than 50 % by weight.The boiling range of light gasoline fraction is between 35～85 ℃.
Refining shale heavy oil in catalytic cracking reaction device with catalyst for cracking contact reacts after, reclaimable catalyst is introduced revivifier regeneration after introducing stripper stripping, reaction product (oil gas product) is introduced fractionating system, and separation can obtain low-carbon alkene, gasoline, diesel oil, heavy oil and other low molecule saturated hydrocarbons.The method of fractionation is prior art, and the present invention repeats no more.The C4 alkene that separation obtains and final boiling point can be introduced fluidized bed reaction zone or riser reaction zone or introduce second burst of regenerated catalyst (transfer limes reactor) reaction lower than the gasoline of 85 ℃, to improve the productive rate of propylene, be the productive rate that can also improve light aromatic hydrocarbons (BTX) unexpectedly.The boiling range that separation obtains is that 145～230 ℃ of heavy naphthas can be introduced riser reaction zone or fluidized bed reaction zone further to improve the productive rate of light aromatic hydrocarbons.
In method for processing shale oil provided by the invention, for reducing the oil gas dividing potential drop in refining shale catalytic conversion of heavy oil reaction, to injecting one or more the thinner that is selected from water vapour, nitrogen and C1～C4 alkane in described catalytic cracking reaction device, preferred thinner is water vapour, the weight ratio of water vapour and refining shale heavy oil feedstock is 0.01～2: 1, is preferably 0.01～1: 1.
In method for processing shale oil provided by the invention, the pyrolysis gasoline cut fraction that the refining shale heavy oil catalytic pyrolysis of the present invention is obtained contacts in adsorptive reactor with sorbent material, sulphur content and nitrogen content in gasoline fraction are reduced, and the sorbent material after contact is introduced the regeneration of catalytic pyrolysis revivifier.Described contact can be carried out in fluidized-bed reactor, the temperature of contact is preferably 220～360 ℃, the pressure of reaction zone (adsorptive pressure) is preferably 0.2～0.9MPa (absolute pressure), and the weight ratio of sorbent material and gasoline is preferably 1～25, and the weight hourly space velocity of raw material is preferably 0.5～8h
-1.The boiling range of described gasoline fraction is between 35 ℃～230 ℃, can be full distillation gasoline (boiling range is 35～230 ℃), also can be part distillation gasoline, described part distillation gasoline is the gasoline fraction of boiling range between 75～155 ℃ for example, its initial boiling point can be 75～85 ℃, and final boiling point can be 145～155 ℃.Because described sorbent material is catalytic cracking catalyst, with first strand of catalytic cracking catalyst be same catalyzer, therefore in the sorbent material rear introducing cat-cracker revivifier separated with gasoline after contact, do not need to increase the regenerating unit of sorbent material.Conventionally, sorbent material comprises regeneration catalyzing catalyst for cracking, can certainly contain fresh catalytic cracking catalyst.
In the working method of the shale oil of confession of the present invention, in the gasoline fraction after absorption, sulphur content and nitrogen content reduce greatly, and especially the reduction of nitrogen content has obtained unexpected effect.Because the nitrogen content in refining shale heavy oit pyrolysis gasoline is higher, even can reach 400 μ g/g, (hydrogenating materials nitrogen content is no more than 100 μ g/g to common hydrofinishing process for such gasoline conventionally.) cannot make nitrogen wherein remove completely, thereby be difficult to meet the requirement of further processing, and further improve hydrorefined severity, can make aromatic saturation wherein, when utilizing shale oil recovery light aromatic hydrocarbons, this aromatic saturation can cause target product yield to reduce.And gasoline fraction sulphur content and the nitrogen content of the present invention after absorption significantly reduces, while carrying out hydrogenation, can under comparatively gentle condition, operate, be more easily met the pyrolysis gasoline of follow-up solvent extraction requirement.
In the working method of shale oil provided by the invention, can also comprise that (the present invention also claims refining with adsorbents by absorption denitrogenation, the gasoline of absorption after denitrogenation is called refining with adsorbents gasoline) after boiling range be 75～155 ℃ of preferably gasoline fraction hydrofinings of 85～145 ℃, then carry out solvent extraction; Or the boiling range by absorption after denitrogenation is the gasoline fraction hydrofining of 35～230 ℃, by the boiling range after hydrofining, be then 75～155 ℃ preferably the gasoline fraction of 85～145 ℃ carry out solvent extraction.Described hydrofining can be carried out according to existing method, comprise the gasoline fraction after absorption denitrogenation is contacted with hydrogenation catalyst, hydrogen, at hydrogen dividing potential drop 2.0～15.0MPa, 200～400 ℃ of temperature of reaction, hydrogen to oil volume ratio 100v/v～1000v/v, volume space velocity 0.5～5h
-1condition under, by olefin saturated wherein, remove the impurity such as sulphur, nitrogen simultaneously, obtain being rich in the refining heavy petrol of light aromatic hydrocarbons.Described hydrogenation catalyst can be VIB and/or the VIII family non-precious metal catalyst loading on aluminum oxide and/or amorphous silicon aluminium, and described VIB base metal is selected from Mo or/and W, and VIII family base metal is selected from Co or/and Ni.Preferred hydrogenation catalyst be by one or more group VIII metals of 0～10 % by weight additive, 1～9 % by weight, one or more group vib metals of 12～39 % by weight and surplus aluminum oxide and/or amorphous silicon aluminium carrier form, wherein said additive is selected from non-metallic element and the metallic elements such as fluorine, phosphorus, titanium.Hydrofining can referenced patent CN94102955, CN200310121166, CN200310121167, CN200310121168.Described solvent extraction can be according to existing method, and the solvent of solvent extraction is selected from tetramethylene sulfone, N-Methyl pyrrolidone, diethylene glycol ether, triethylene glycol ether, TEG, dimethyl sulfoxide (DMSO) and N-formyl morpholine ether one or more mixed solvent; After solvent recuperation, recycle; The light aromatic hydrocarbons that solvent-extracted oil obtains one of the object of the invention product by further separation is benzene, toluene and dimethylbenzene, and raffinating oil is that non-aromatics can be used as steam crack material, also can return to riser reactor and carry out scission reaction.The temperature of solvent extraction is 80～120 ℃, and the volume ratio between solvent and gasoline is 2～6.Solvent extraction can referenced patent CN1393507A, CN1258717A.
In the working method of shale oil provided by the invention, also comprise hydrogenation of shale oil is refined, then separation obtains refining shale light oil and refining shale heavy oil.Wherein, described hydrofining comprises the step of shale oil, hydrogen and hydrogenation catalyst contact, hydrorefined reaction pressure 7.0～25.0MPa, and 370～450 ℃ of temperature of reaction, volume space velocity is 0.2～1.2h
-1hydrogen to oil volume ratio 500～4000: 1, described hydrogenation catalyst can be VIB and/or the VIII family non-precious metal catalyst loading on aluminum oxide and/or amorphous silicon aluminium, and described VIB base metal is selected from Mo or/and W, and VIII family base metal is selected from Co or/and Ni.After described hydrogenation of shale oil, obtain refining shale oil (hydrogenation reaction generates oil), refining shale oil nitrogen content is preferably no more than 0.5 % by weight, and sulphur content is no more than 0.5 % by weight.Refining shale oil obtains refining shale light oil and refining shale heavy oil through separation, and wherein the initial boiling point of refining shale heavy oil is not less than 300 ℃, is preferably not less than 350 ℃, and preferably the boiling range of shale heavy oil is between 350～750 ℃.The described hydrogenation of shale oil that makes is refining, and then separation obtains refining shale light oil and refining shale heavy oil, can reference CN101492605A, CN1011067089A.
A kind of cat-cracker for shale oil processing provided by the invention as shown in Figure 2, comprise riser reaction zone (riser reactor) 1, fluidized bed reaction zone (fluidized-bed reactor) 3, catalyst transfer line 2, catalyst transfer line 11, settling vessel 4 and stripper 5, wherein said stripper 5 is positioned at the below of described fluidized bed reaction zone 3, and described stripper 5 is directly communicated with the bottom of described fluidized bed reaction zone 3, the optional position of the bottom of the outlet of described riser reaction zone 1 and described fluidized bed reaction zone 3 is communicated with, the oil gas vent of fluidized bed reaction zone 3 is communicated with settling vessel 4 and is communicated with the entrance of gas-solid separation equipment 41 in settling vessel, described catalyst transfer line 2 is for the regenerated catalyst of revivifier 6 is delivered to fluidized bed reaction zone 3, and described catalyst transfer line 11 is for being delivered to the regenerated catalyst of revivifier 61 bottom, riser reaction zone.Preferably, described settling vessel 4 is coaxial with described fluidized bed reaction zone 3, and be positioned at described fluidized bed reaction zone 3 directly over; Described stripper 5 is coaxial with described fluidized bed reaction zone 3, and be positioned at described fluidized bed reaction zone 3 under.Because stripper 5 is communicated with fluidized bed reaction zone 3 gas-solids, therefore, by regulating stripper 5, to revivifier 6, discharge the flowrate control valve of reclaimable catalyst, can directly control the material level of catalyzer in fluidized bed reaction zone, and then the weight hourly space velocity of reaction in control fluidized bed reaction zone, can increase thus the technique flexibility ratio of catalytic cracking reaction.In the present invention, make stripper be positioned at the below of fluidized bed reaction zone, and stripper is communicated with the bottom of fluidized bed reaction zone.Thus, to the water vapour of supplying in stripper, can upwards by fluidized bed reaction zone, as the water filling steam that catalytic cracking reaction wherein occurs, obtain second stage employ, be conducive to reduce the overall energy consumption of reaction.Described riser reaction zone be selected from molectron that isodiametric pipe, taper type cylindrical shell or the different straight barrel of 1-6 section diameter be formed by connecting by reducer at least any; Described fluidized bed reaction zone be selected from molectron that isodiametric cylindrical shell, taper type cylindrical shell or the different straight barrel of 1-6 section diameter be formed by connecting by reducer at least any.Described riser reaction zone can be the one or more of parallel connection, and when being a plurality of, described at least one, riser reaction zone is positioned at the outside of described stripper; A described riser reaction zone is passed the inside of described stripper and is communicated with the bottom of described fluidized bed reaction zone at the most.Revivifier 6 is for the catalyzer of the catalytic pyrolysis of having regenerated, described catalyst regenerator is communicated with respectively by least one regenerated catalyst with described riser reaction zone, revivifier is communicated with respectively by least one regenerated catalyst with described fluidized bed reaction zone, and, described catalyst regenerator is communicated with described stripper by least one reclaimable catalyst transfer lime, and catalyst stream control valve is installed on transfer lime described at least one.
The following examples will be further described the present invention, but therefore not limit the present invention.Test is to carry out on medium-sized tester.
In embodiment, take total catalyst weight as benchmark, used catalyst is containing 10 % by weight β zeolites, 20 % by weight ZRP-1 zeolites, 45 % by weight kaolin and 25 % by weight alumina binder; Wherein β zeolite, ZRP-1 zeolite are catalyzer asphalt in Shenli Refinery of China Petrochemical Industry product, and β Zeolite is 30, contain in the iron of element 1 % by weight, the phosphorus of 1.5 % by weight; The silica alumina ratio of ZRP-1 zeolite is 40, contains in element 1.1 % by weight P, 1.1 % by weight rare earths.This method for preparing catalyst comprises: kaolin, pseudo-boehmite and deionized water are mixed to making beating, make the slurries that solid content is 30 % by weight, then the pH value that adds hydrochloric acid (concentration is 25 % by weight) adjusting slurries is 3, be warming up to 50 ℃, stir lower aging 30 minutes, then add zeolite slurry (content of slurries mesolite is 30 % by weight), stir 15 minutes, the dry catalyzer that obtains of spraying.Catalyzer under 800 ℃, 100% water vapour atmosphere aging 10 hours, in device, the loading amount of catalyzer is 60 kilograms.Use medium-sized tester, as shown in Figure 2, the internal diameter (diameter) of riser reaction zone (reactor) 1 is 16 millimeters, 5 meters of height, the internal diameter of fluidized bed reaction zone (reactor) 3 is 64 millimeters, 0.5 meter of height, 300 millimeters of settling vessel 4 internal diameters, the outlet of catalyst transport 2 is 0.2 meter of on top, fluidized bed reaction zone.
Effect when embodiment 1～4 explanation adopts refining shale heavy oil feedstock catalysis conversion method provided by the invention.Its flow process as shown in Figure 2, wherein in riser reaction zone 1 reacted oil gas with catalyzer without 3 bottoms, separated direct introducing fluidized bed reaction zone, in fluidized bed reaction zone 3, proceed reaction; In fluidized bed reaction zone 3, catalyzer leaves from bottom and enters stripper 5, oil gas leaves from the top of fluidized-bed reactor, enter settling vessel 4, dilution water steam is introduced at 1 the middle part from riser reaction zone (height 1/2), and second strand of catalytic cracking catalyst is from the introducing fluidized bed reaction zone, top 3 of fluidized-bed reactor 3 beds; The water stripping steam consumption of stripper is 3 % by weight of refining shale heavy oil feedstock, and from fluidized bed reaction zone, 3 bottom enters fluidized bed reaction zone to stripping oil gas, through behind fluidized bed reaction zone, enters settling vessel.The character of refining shale heavy oil feedstock is in Table 1, and evaluation result is in Table 2.In table 2, reaction zone A refers to that riser reaction zone 1, B refer to that transfer lime 2, C refer to fluidized bed reaction zone 3.Agent-oil ratio refers to introduces the catalyzer of reactor and the weight ratio of fresh feed (refining shale heavy oil feedstock).Settling vessel top pressure is 0.2MPa.
As Fig. 2, refining shale heavy oil feedstock (character is in Table 1) is introduced riser reaction zone 1 and first burst of catalyzer contact reacts introducing riser reaction zone 1; Second strand of catalyzer introduced fluidized bed reaction zone 3 by catalyst transport 2.The reaction conditions of each reactor and the results are shown in Table 2.
Refining shale heavy oil feedstock (character is in Table 1) enters riser reaction zone 1 and first burst of catalyzer contact reacts introducing riser reaction zone 1, freshening C4 hydrocarbon (olefin(e) centent is 50 % by weight) enters catalyst transport 2 (now transfer lime also can claim transfer limes reactor), and causes top, fluidized bed reaction zone together with after second burst of catalyzer contact reacts in introducing transfer lime 2.Reaction conditions and the results are shown in Table 2.The weight ratio of freshening C4 hydrocarbon and refining shale heavy oil feedstock is 0.15: 1.
Refining shale heavy oil feedstock (character is in Table 1) enters riser reaction zone 1, (boiling range is 35～85 ℃ for freshening C4 hydrocarbon (olefin(e) centent is 50 % by weight) and petroleum naphtha component, olefin(e) centent is 50 % by weight) enter transfer lime 2, introduce the top (from introducing fluidized bed reaction zone, top 3) of fluidized bed reaction zone 3 together with after the regeneration catalyst for cracking contact reacts of introducing transfer lime 2.The weight ratio of C4 hydrocarbon and petroleum naphtha is 1.5: 1; The weight ratio of the gross weight of freshening C4 hydrocarbon and petroleum naphtha and refining shale heavy oil feedstock is 0.25: 1.
Embodiment 4
According to the method for embodiment 1, difference is that boiling range that split product fractionation is obtained is that the gasoline fraction of 35～230 ℃ contacts and carries out after absorption reaction with sorbent material (regeneration catalyst for cracking), and the sorbent material that separation obtains is introduced cat-cracker revivifier.From reaction result, the catalyzer after absorption returns to cat-cracker, does not make reaction effect variation, still keeps higher propylene and light aromatics yield.Described adsorption desulfurize carries out in fluidized-bed reactor, and gasoline and sorbent material are introduced to fluidized-bed reactor bottom, at 300 ℃, agent-oil ratio (weight ratio of sorbent material and gasoline), is then 3: 1, weight space velocity 2.5h
-1, pressure is under 0.7MPa, to carry out absorption reaction, leaves after fluidized-bed reactor separatedly, and the catalyzer after absorption returns to cat-cracker revivifier, and the gasoline recovery after absorption obtains refining with adsorbents gasoline.After absorption, the sulphur content of gasoline is that 50 μ g/g nitrogen contents are 80 μ g/g.
Comparative example 1
Illustrate that adopting riser tube to add fluidized-bed reactor carries out heavy oil feedstock catalyzed conversion, referring to embodiment 1, does not introduce second strand of catalyzer as different from Example 1.The results are shown in Table 2.
Table 1
From table 2, in method for processing shale oil provided by the invention, there is than existing methods higher productivity of propylene and light aromatics yield, and can reduce sulphur and the nitrogen content in pyrolysis gasoline.
Effect while adopting catalytic cracking gasoline adsorbent desulfurizing and denitrifying method provided by the invention is described.
The pyrolysis gasoline that refining shale heavy oit pyrolysis is obtained contacts in small-sized fluidized bed reactor (treatment capacity is 0.5L gasoline/h) with catalytic cracking catalyst (catalyst for cracking provided by the invention), carry out absorption reaction, then by the two separation, obtain the gasoline (refining with adsorbents gasoline) after catalyzer after separation and absorption, before and after the condition of absorption reaction, absorption, the sulphur content of gasoline stocks, nitrogen content are in Table 3.
Table 3
| |
|
Embodiment 7 | Embodiment 8 | |
| Feed gasoline sulphur content, μ g/g | 120 | 120 | 120 | 120 |
| Feed gasoline nitrogen content, μ g/g | 350 | 350 | 350 | 350 |
| Adsorption temp, ℃ | 230 | 270 | 310 | 350 |
| Adsorptive pressure, MPa | 0.3 | 0.5 | 0.6 | 0.8 |
| Agent-oil ratio | 20 | 15 | 10 | 1 |
| Weight hourly space velocity, h -1 | 0.8 | 3 | 4.2 | 6.5 |
| Yield of gasoline, % | 99.1 | 99.2 | 99.3 | 99.4 |
| Refining with adsorbents content of sulfur in gasoline, μ g/g | 55 | 49 | 51 | 45 |
| Refining with adsorbents gasoline nitrogen content, μ g/g | 86 | 78 | 75 | 72 |
In table 3, agent-oil ratio refers to the weight ratio of the gasoline fraction of the sorbent material introduced in adsorptive reactor and introducing, and adsorptive pressure refers to adsorptive reactor top pressure, and adsorption temp refers to the bed temperature of fluidized-bed.
From table 3, adsorption refining method of the present invention, nitrogenous compound and sulfocompound in can effective elimination catalytic cracking gasoline, reduce sulphur content and nitrogen content in gasoline, meet the requirement of catalytic cracking gasoline selective hydrogenation, thereby can reduce hydrorefined load; In addition, the yield of gasoline is higher, can reach more than 99%.
Although above, by embodiment, the present invention is had been described in detail, it is to be noted, various distortion are apparent to those skilled in the art.Therefore, these distortion should comprise in the present invention, unless these distortion have exceeded scope of the present invention.
Claims (13)
1. the working method of a shale oil, comprise: make refining shale heavy oil contact and carry out catalytic cracking reaction with first strand of catalytic cracking catalyst in catalytic cracking reaction device, reaction product is introduced to fractionating system separation, and reacted catalyzer is introduced the regeneration of catalytic cracking catalyst revivifier after stripping; The gasoline fraction that fractionating system separation is obtained and sorbent material are that 200～400 ℃, pressure are that the weight ratio of 0.1～1.0MPa, sorbent material and gasoline fraction is 0.5～50, the weight hourly space velocity of gasoline fraction is 0.1～10h in temperature
-1lower contact, the sorbent material after contact is separated with gasoline, and the sorbent material after separation is introduced described catalytic cracking catalyst revivifier, and described sorbent material is catalytic cracking catalyst, and the boiling range of described gasoline fraction is between 35～230 ℃.
2. in accordance with the method for claim 1, it is characterized in that, described catalytic cracking reaction device comprises at least two reaction zones, the first reaction zone is riser reaction zone, second reaction zone is fluidized bed reaction zone, and refining shale heavy oil is introduced fluidized bed reaction zone with first strand of catalytic cracking catalyst and reacted after the contact reacts of riser reaction zone; The reacted oil gas in fluidized bed reaction zone is introduced fractionation plant through settling vessel, and reclaimable catalyst is introduced stripper stripping.
3. in accordance with the method for claim 2, it is characterized in that, described fluidized bed reaction zone and riser reaction zone just arrange, fluidized bed reaction zone is on riser reaction zone, and the reacted oil gas in riser reaction zone and catalyzer are from the introducing fluidized bed reaction zone, bottom of fluidized bed reaction zone; In fluidized bed reaction zone, reacted reclaimable catalyst is drawn from the bottom of fluidized bed reaction zone, and oil gas is from the Base top contact of fluidized bed reaction zone; From the top of fluidized bed reaction zone, also introduce second strand of catalytic cracking catalyst, second strand of catalytic cracking catalyst is 2～10:1 with the weight ratio of introducing the refining shale heavy oil of the first reaction zone.
4. in accordance with the method for claim 2, it is characterized in that, the temperature of reaction of carrying out described catalytic cracking reaction in described riser reaction zone is 480-620 ℃, and agent-oil ratio is 5～20, and the reaction times is 0.1～6 second; The temperature of reaction of carrying out described catalytic cracking reaction in described fluidized bed reaction zone is 480-630 ℃, and agent-oil ratio is 8～40, and weight hourly space velocity is 0.2-30h
-1.
5. in accordance with the method for claim 3, it is characterized in that, second strand of described catalytic cracking catalyst is by the catalyzer obtaining after regenerated catalyst and/or live catalyst and C4～C8 hydrocarbon contact reacts, wherein 520～680 ℃ of catalytic temperature of reaction, agent-oil ratio 10～50, reaction times 0.05～4s.
6. in accordance with the method for claim 1, it is characterized in that, described gasoline fraction be boiling range be 35～230 ℃ whole distillation gasolines or for boiling range be the part distillation gasoline of 75～155 ℃.
7. in accordance with the method for claim 1, it is characterized in that, also comprise the gasoline fraction hydrofining after contacting with sorbent material.
8. in accordance with the method for claim 7, it is characterized in that, also comprise that the hydrofined gasoline that described hydrofining is obtained carries out solvent treatment.
9. in accordance with the method for claim 1, it is characterized in that, described sorbent material, first strand of catalytic cracking catalyst and second strand of catalytic cracking catalyst are catalytic cracking catalyst of the same race.
10. according to the method described in claim 1,2,3,4,5,8 or 9, it is characterized in that the β zeolite that described catalytic cracking catalyst contains modification.
11. in accordance with the method for claim 1, it is characterized in that, the gross weight of catalyzer of take is benchmark, zeolite mixture, the heat-resistant inorganic oxide of 5～99 % by weight and the clay of 0～70 % by weight that the catalytic cracking catalyst of the described β zeolite containing modification contains 1～60 % by weight; The gross weight of described zeolite mixture of take is benchmark, in described zeolite mixture, contain 1～75 % by weight by the β zeolite of phosphorus and transition metal M modification and the zeolite with MFI structure of 25～99 % by weight; Described transition metal M is selected from one or more in Fe, Co, Ni and Cu.
12. in accordance with the method for claim 1, it is characterized in that, also comprises hydrogenation of shale oil is refined, the shale oil separation after hydrofining is obtained to refining shale heavy oil; Described hydrofining operational condition: reaction pressure 7.0～25.0MPa, 370～450 ℃ of temperature of reaction, volume space velocity 0.2～1.2h
-1, hydrogen to oil volume ratio 500～4000:1.
13. a process for purification for nitrogenous pyrolysis gasoline, comprises by gasoline fraction and sorbent material being that 200～400 ℃, pressure are that the weight ratio of 0.1～1.0MPa, sorbent material and gasoline fraction is 0.5～50, the weight hourly space velocity of gasoline fraction is 0.1～10h in temperature
-1lower contact, the sorbent material after contact is separated with gasoline, and the sorbent material after separation is introduced revivifier regeneration; Described sorbent material is catalytic cracking catalyst, and the boiling range of described gasoline fraction is between 35～230 ℃.
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